JP2002128898A - Method for producing inorganic polymer compound, inorganic polymer compound, and inorganic polymer compound film - Google Patents

Abstract

(57) [Problem] It is desired to provide a method for producing an inorganic polymer compound, which can form a film having various functions such as improved wettability to a substrate, adhesion, and corrosion resistance. SOLUTION: A Zr alkoxide and / or a B alkoxide is used in an amount of 0.05 to 0.about.1 mole among two or more moles selected from a tetraalkylsilicate, an alkylalkoxysilicate and a silica condensation polymer.
And 2 mol, 0.01 to the silica sol in terms of SiO ₂
0.3 mol, acid and / or metal salt in 1/100 to 1
/ 30 mol and water and / or acetic acid with 1-4 mol,
And a method of producing an inorganic polymer compound in which, after preparing a hydrophilic organic solvent, a part or all of the raw materials are refluxed, and finally the whole is mixed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an inorganic polymer compound, and more particularly, to a method of forming a coating such as a metal oxide on a substrate such as glass, metal (stainless steel, copper, aluminum, etc.), and ceramics. And a method for producing an inorganic polymer compound, an inorganic polymer compound, and an inorganic polymer compound film.

[0002]

2. Description of the Related Art Conventionally, as inorganic polymer compounds, silica condensation polymers using tetraethoxysilicate or alkylalkoxysilicate, compositions obtained by condensation polymerization reaction using Zr alkoxide or Ti alkoxide, Many are known, including those obtained by using various metal alkoxides in combination. However, although these inorganic high molecular compounds have been devised and used depending on the purpose, no single composition having properties that can be used for all purposes has been obtained.

In addition, such a method for producing an inorganic high molecular compound involves only partial hydrolysis and polycondensation, and the reaction is single. However, the properties of the obtained inorganic polymer compound vary greatly depending on the material, reaction procedure, and the like, as is well known.

For example, a silica-based polymer compound is usually subjected to a hydrolysis reaction or a polycondensation reaction using tetraethoxysilicate, alkylalkoxysilicate, or a compound which has been polycondensed to some extent.
The objective polymer compound is obtained. However, the polymer compound thus obtained has a particularly low corrosion resistance to alkalis, and therefore, the improvement is achieved by the addition of other elements.

Further, titanium which is corrosion-resistant as an oxide,
In the case of zirconium and the like, the reactivity of the raw material alkoxide is high, and therefore, it is common to add a chelating agent such as acetylacetone or alkanolamine to suppress the reactivity, and then to cause a hydrolysis reaction or a condensation polymerization reaction. The way has been. In this case, at a temperature of 300 ° C. or less, an organic chelating agent is contained in the obtained inorganic polymer compound.

Inorganic polymer compounds such as silicon, titanium, and zirconium produced using metal alkoxide as a raw material are coated on a substrate of glass, ceramics, metal (the surface of which is a thin oxide) to form a film. Done. In the film thus obtained, a high adhesion strength between the substrate and the substrate can be obtained by chemically bonding the silanol groups on the surface to the substrate surface. However, in the case of a compound having few or no silanol groups on the surface, the adhesion strength of the obtained film is reduced.

Others such as sodium silicate and lithium silicate, which are similar to so-called water glass, are well known as inorganic high molecular compounds.
Although these are used as materials for inorganic coatings, they have the disadvantage of dissolving in water. Also in these cases, although the properties are improved by adding other elements, satisfactory ones have not been obtained yet.

[0008]

By the way, an inorganic polymer compound using a metal alkoxide as a raw material is produced by utilizing a hydrolysis reaction and a polycondensation reaction.
Therefore, these inorganic high molecular compounds are useful materials for forming a film by being applied to a substrate and dried or fired. However, depending on the type of the substrate, and the type and condition of the surface of the substrate and the obtained film, the wettability when applying the inorganic polymer compound to the substrate is poor, and the film properties such as adhesion and hardness of the obtained film are poor. It can be very different.

In addition, although a relatively strong corrosion resistance of the formed film can be obtained with an acid, many of the films are weak with an alkali, and development of an inorganic polymer compound having corrosion resistance is expected. Further, although an inorganic polymer compound can be used as a binder for the inorganic pigment powder, in such a case, depending on the type of the inorganic pigment powder, aggregation or a decrease in the function of the inorganic pigment powder may occur.

The present invention has been made in view of the above circumstances, and an object of the present invention is to select the type of metal alkoxide and control the addition method and temperature in a hydrolysis reaction or a polycondensation reaction. An object of the present invention is to provide an inorganic polymer compound, a method for producing the same, and an inorganic compound film obtained by the method, which can form a film having various functions such as improvement in wettability to a substrate, adhesion, and corrosion resistance.

[0011]

The process for producing an inorganic polymer compound of the present invention is represented by the general formula Si (OR ¹ ) ₄ : wherein R ¹ represents an alkyl group having 1 to 4 carbon atoms. With a tetraalkyl silicate represented by the general formula R ² Si (OR ³ )
₃ : (wherein R ² Is an alkyl group having 1 to 8 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms), and a total mole number of two or more kinds selected from an alkyl alkoxysilicate and a silica condensation polymer. Formula 1 Zr (OR ⁴ ) ₄ : (wherein R ⁴ has 2 to ⁴ carbon atoms)
And / or a Zr alkoxide represented by the general formula B (OR ⁵ ) ₃ : wherein R ⁵ has 1 to 1 carbon atoms.
B alkoxide represented by the following formula ( ₂ ): 0.05 to 0.2 mol; silica sol: 0.01 to 0.3 mol in terms of SiO ₂ ; acid and / or metal salt: 1/100 After preparing モ ル 1/30 mol, water and / or acetic acid 1-4 mol, and a hydrophilic organic solvent, these materials are partially or entirely refluxed, and finally the entire amount is mixed. What has been achieved is a means for solving the above problem.

[0012] Further, the inorganic polymer compound of the present invention is obtained by the above-mentioned production method as a means for solving the above-mentioned problem. Further, in the inorganic polymer compound film of the present invention,
The means for solving the above-mentioned problem is that the inorganic polymer compound is a film formed by being applied on a substrate, dried and / or fired.

Hereinafter, the present invention will be described in detail. In the above, in the tetraalkyl silicate represented by the general formula Si (OR ¹ ) ₄ , R ¹ is an alkyl group having 1 to 4 carbon atoms, and is any one of a methyl group, an ethyl group, a propyl group, and a butyl group. . Specific examples of such a tetraalkyl silicate include tetramethoxy silicate, tetraethoxy silicate, tetrapropoxy silicate, and tetrabutoxy silicate. Preferred are tetramethoxysilicate and tetraethoxysilicate.

The general formula R^TwoSi (OR^Three)_ThreeA represented by
The alkylalkoxysilicate is represented by R ^TwoHas 1 to 8 carbon atoms
Alkyl group, specifically, a methyl group, an ethyl group,
Propyl group, butyl group, vinyl group, γ-glycidoxypro
Pill group, γ-methacryloxypropyl group, aminopro
Pill group, phenyl group and the like. Also, R^ThreeIs the carbon number
1-4 alkyl groups, a methyl group, an ethyl group,
It is either a pill group or a butyl group.

Specific examples of such an alkylalkoxysilicate include methyltrimethoxysilicate, methyltriethoxysilicate, ethyltrimethoxysilicate, ethyltriethoxysilicate, propyltrimethoxysilicate, propyltriethoxysilicate, butyltrimethoxysilicate, Butyl triethoxy silicate, vinyl trimethoxy silicate, vinyl triethoxy silicate, γ-glycidoxy propyl trimethoxy silicate, γ-glycidoxy propyl triethoxy silicate, γ-methacryl propoxy trimethoxy silicate, γ-methacryl propoxy triethoxy silicate , Phenyltrimethoxysilicate, phenyltriethoxysilicate, 3-aminopropyltrimethoxysilicate , And the like 3-aminopropyltriethoxysilane silicate. Preferably,
Methyltrimethoxysilicate, methyltriethoxysilicate, γ-glycidoxypropyltrimethoxysilicate, γ-methacrylpropoxytrimethoxysilicate, and 3-aminopropyltrimethoxysilicate.

Examples of the silica polycondensate include those obtained by partially condensing tetramethyl silicate, tetraethyl silicate, and the like, and commercially available products such as ethyl silicate 40 and MS5
1 (manufactured by Mitsubishi Chemical Corporation) or the like can be used.

As the above-mentioned raw materials, at least two or more selected from three kinds of tetraalkyl silicate, alkylalkoxy silicate and silica condensation polymer are used. The raw materials other than those described below are used based on the total number of moles (total number of moles).

In such raw materials, when the obtained inorganic polymer compound is used for forming a film on a substrate, in order to improve the adhesion to the substrate, an alkylalkoxysilicate should be used according to the type of the substrate. And select as appropriate. For example, when there are few silanol groups on the substrate surface, among the alkylalkoxysilicates, γ-glycidoxypropyltrimethoxysilicate, γ-methacrylpropoxytrimethoxysilicate, 3-aminopropyltrimethoxysilicate, and the like have a large addition effect and are suitable. It is said. The addition amount of such an alkylalkoxysilicate is 1/1 of the addition amount of the entire raw material.
0 or less is desirable. If it exceeds 1/10, wettability to the substrate may be deteriorated during film formation.

In order to increase the hardness of the film, it can also be improved by promoting the hydrolysis or polycondensation reaction to increase the degree of hydrolysis and the degree of polycondensation. Thus, in the present invention, the improvement can be achieved by increasing the amount of a tetraalkyl silicate (for example, tetramethyl silicate) or a silica condensation polymer in the raw material, or by adding colloidal silica which is a fine particle of the raw material described later. be able to. It should be noted that excessive addition of colloidal silica may be a factor in inhibiting film formation, so care must be taken in the amount of addition.

In the above, the general formula Zr (OR^Four)_Four
The Zr alkoxide represented by ^FourHas 2 to 4 carbon atoms
Alkyl, ethyl, propyl, butyl
Either. The general formula B (OR^Five)_ThreeRepresented by
B alkoxide is R^FiveIs an alkyl group having 1 to 2 carbon atoms
And is either a methyl group or an ethyl group.

Specific examples of the Zr alkoxide include zirconium tetraethoxide, zirconium tetraisopropoxide, zirconium tetra n-propoxide, zirconium tetra n-butoxide, zirconium tetrasec-butoxide, and zirconium tetratert-butoxide. Preferred are zirconium tetraisopropoxide and zirconium tetra n-butoxide. Specific examples of the B alkoxide include boron methoxide and boron ethoxide.

The use amount (addition amount) of such a raw material is in the range of 0.02 to 0.2 mol, preferably 0.05 to 0.15 mol, per 1 mol of the raw material. That is, the number of moles of the Zr alkoxide and / or the number of moles of the B alkoxide to be used is within the above range with respect to 1 mole of the total moles of the raw material. Is mainly added for improving corrosion resistance. When a Zr alkoxide and a B alkoxide are used in combination, the added amount of the B alkoxide is 1/1 or less with respect to the added amount of the Zr alkoxide. It is desirable that If it exceeds 1/1, the corrosion resistance cannot be sufficiently improved.

The silica sol used as the raw material is generally called colloidal silica, and can be used in either an aqueous system or an organic solvent system. The amount (addition amount) of this raw material is 0.01 to 0.3 mol, preferably 0 mol, per 1 mol of the raw material, that is, 1 mol of the total mol number of the raw material. .01-
The range is 0.2 mol. The raw material is added in order to absorb the distortion of the film and prevent the film from cracking. Note that, although this raw material also has the effect of increasing the strength of the film, as described above, an excessive addition may hinder film formation.

As the raw material acid, hydrochloric acid, nitric acid,
p-Toluenesulfonic acid, among which nitric acid, p-
Toluenesulfonic acid is preferred. Examples of the metal salt include chloride, nitrate, and acetate. Specific examples include zinc chloride, aluminum chloride, titanium tetrachloride, tin tetrachloride, zinc nitrate, bismuth nitrate, and zinc acetate. Among them, zinc nitrate, zinc acetate, bismuth nitrate, titanium tetrachloride, and tin tetrachloride are exemplified. preferable.

The use amount (addition amount) of such a raw material is 1/100 to 1/100 with respect to 1 mole of the raw material, that is, 1 mole of the total mole number of the raw material.
The range is 30 mol, preferably 1/100 to 1/50 mol. The raw material is added as a catalyst for accelerating the polycondensation reaction.It promotes hydrolysis and polycondensation reactions such as alkyl silicates in solution, and promotes the polycondensation reaction during film formation. It is responsible for.

The amount (addition amount) of water and / or acetic acid as the raw material is 1 to 1 mol of the raw material, that is, 1 to 1 mol of the total number of mols of the raw material.
It is in the range of 4 moles, preferably 2-4 moles.

The reactions generally called hydrolysis reaction and polycondensation reaction proceed by the action of water. By controlling these reactions, the generated inorganic polymer compound affects its film forming ability and the properties of the resulting film. For example,
When they have the same composition, it is preferable to cause a uniform hydrolysis reaction and a condensation polymerization reaction. Although it is possible to use 100% of water obtained by the reaction between acetic acid and alcohol, the film-forming ability of the obtained inorganic polymer compound may be deteriorated depending on the combination of materials used.
Preferably, acetic acid and water are used together (complex).
In this case, it is preferable that the (water / acetic acid) ratio be in the range of 20% before and after 1/1. However,
It is possible to produce an inorganic high molecular compound even if one of them is used 100%.

Examples of the organic solvent which is a raw material include methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol and te.
Examples thereof include rt-butanol, 2-methoxyethanol, 2-ethoxyethanol, and 1-methoxy-2-propanol, and any hydrophilic solvent can be used. However, since the selection of the solvent is compatible with the obtained inorganic polymer compound, it is preferable to determine and select the solvent by applying it to a substrate to be actually used. In general, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, and the like having an ether bond contribute to stabilization of a polymer compound and are preferable because they are relatively high-boiling solvents. There are many.

After preparing each of such raw materials, an inorganic high molecular compound is produced using the raw materials as follows.
And at least two of the three selected from the group consisting of tetraalkyl silicate, alkylalkoxysilicate and silica condensation polymer. When the total mole number (total mole number) of all the selected species is converted to 1 mole, for example, 0.3 to 0.6 mole of alkylalkoxysilicate and the total amount of tetraalkylsilicate and silica condensation polymerization (or only one of them) Is 0.7-0.4 mol. The relative ratio between the tetraalkyl silicate and the silica polycondensation can be appropriately selected. Further, the alkylalkoxysilicate is preferably 0.4 to 0.6 mol, and the total amount (or only one amount) of the tetraalkylsilicate and the silica condensation polymer is preferably 0.4 to 0.6 mol, In this case, the relative ratio between the tetraalkyl silicate and the silica polycondensation is preferably set to 1/10 or less.

If the amount of the silica condensation polymer is large, the adhesion of the inorganic polymer compound obtained by adding a metal alkoxide and further causing hydrolysis or condensation polymerization to a substrate may be deteriorated. When the amount of the alkylalkoxysilicate exceeds 0.6 mol, the tendency of the film to have low hardness becomes remarkable. The tetraalkyl silicate and the silica condensation polymer have the property of increasing the strength of the film formed from the obtained inorganic polymer compound.

The starting material is used in an amount of 0.02 to 0.2 mol, preferably 0.05 to 0.15 mol, per 1 mol of the starting material.
Add in molar range. If the amount exceeds 0.2 mol, the stability of the obtained liquid will deteriorate, and if it is less than 0.02 mol, the corrosion resistance of the film formed from the obtained inorganic polymer compound will deteriorate. That is, the raw material is added for the corrosion resistance of the film, and the amount added is preferably determined by confirming the corrosion resistance of the obtained inorganic polymer compound. The addition amount of the Zr alkoxide is within a range that can be used without adding a stabilizer such as a chelating agent because of its high reactivity with water. The range is 0.2 mol or less with respect to 1 mol of the number (total mol number).

The raw material for the raw material is 1/1 / mol of the total number of moles of the raw material (total mole number).
100 to 1/30 mol, preferably 1/100 to 1/5
Add in a range of 0 mol. If it exceeds 1/30 mol, it may not be dissolved in the reaction solution, or the reaction may be accelerated to cause gelation or precipitation. If it is less than 1/100 mol, the hydrolysis reaction due to addition may occur. This is because acceleration of the polycondensation reaction is not sufficiently recognized.

Further, water and / or acetic acid, which are the starting materials, are used in an amount of 1 to 4 moles, preferably 2 to 4 moles, per mole of the total number of moles (total moles) of the starting materials. Add in. If it exceeds 4 mol, the stability of the resulting mixture tends to be poor, and in some cases, it may gel at the reaction stage. If the amount is less than 1 mol, the polycondensation reaction is not sufficiently performed, and the obtained inorganic polymer compound has poor wettability to the substrate and the adhesion of the film obtained after drying and firing is deteriorated. Although the ratio of water to acetic acid is arbitrary, it is particularly preferable to set the (water / acetic acid) ratio in the range of 0.3 to 0.7. Although it can be used even if it is out of this range, it is not preferable because the wettability to the substrate is deteriorated, and particularly when there is much water, it may be gelled.

And mixed with an organic solvent of
The oxide concentration of the mixture obtained is 2 to 20 wt%, preferably
After adjusting to 5 to 15 wt%, the mixture is refluxed.
The reflux temperature is appropriately set according to the organic solvent used.
However, it is basically reduced at a temperature near the boiling point of the mixed system.
Perform flow operation. The reflux time is determined by IR measurement.
1200cm which is the skeleton vibration of silica ^-1~ 1000cm
^-1It is performed by confirming the absorption peak in the range of
3-4 hours. The absorption peak depends on the material used.
So different.

Next, the starting material is used in an amount of 0.01 to 1 mol per mol of the total number of moles of the starting material (total number of moles).
0.3 mol, preferably 0.01 to 0.2 mol, is prepared, diluted with an organic solvent to 5 to 20 wt%, and added to the above-mentioned reflux. Amount of the raw material is 0.01 to
The reason why the amount is preferably 0.2 mol is that if it exceeds 0.2 mol, the solution becomes cloudy or a precipitate is formed. This is because no improvement in the hardness of the film formed from the obtained inorganic polymer compound can be recognized.

After the addition of the raw materials as described above, the reflux is further continued. The end point of the reaction is determined by confirming an absorption peak which is a skeleton vibration of silica by IR measurement. When tetraethyl silicate was used as a raw material of the compound, the absorption peak was confirmed at around 1200 cm ^-1 . When this was not used, 1020 c by alkylalkoxysilicate or silica condensation polymer was used.
Confirm by the absorption peak near m ^-1 .

The reaction procedure is not particularly limited to the above-mentioned procedure, as long as the reaction proceeds in a homogeneous liquid state, and the procedure may be changed as appropriate. For example, after the raw materials are mixed, the raw materials are added, and a part of the raw materials is further added. Subsequently, by adding an organic solvent, the concentration of the obtained mixture is adjusted so as to be 15 to 5 wt% in terms of oxide, and a reflux treatment is performed in this state.

Next, the raw material is mixed with an organic solvent at 10 wt%.
And add it to the above reflux. Further, the remainder of the raw material is added thereto, and the reflux is continued. Regarding the end point of the reaction, as in the case of the previous reaction procedure, the absorption peak which is the skeletal vibration of silica, ie, 1
Absorption peak around 200 cm ^-1 or 1020c
This is performed by confirming the absorption peak near m ^-1 .

Alternatively, for example, the raw materials may be mixed and then refluxed, further raw materials may be added, and the subsequent raw materials may be added and refluxed. Alternatively, the raw material and a part of the raw material may be mixed and refluxed, the raw material may be added, and then the remainder of the raw material may be added and refluxed. In each case, the reaction end point is determined by confirming the peak of the skeleton vibration of silica by IR measurement.

As described above, in the method for producing an inorganic compound of the present invention, as long as the raw materials are a homogeneous solution, they can be produced by arbitrarily mixing them. Further, by dispersing the inorganic pigment powder in the inorganic polymer compound of the present invention obtained by this production method, applying the obtained dispersion coating liquid to a substrate, and drying and / or baking, these inorganic pigments can be dispersed. An inorganic film, that is, an inorganic polymer compound film can be obtained. Here, as the inorganic pigment powder, iron oxide, zinc oxide, titanium oxide, silica, aluminum oxide, and zinc oxide, indium oxide, and the like, which are conductive inorganic powders, are used. In addition, the inorganic polymer compound can also be formed by applying it alone to various substrates and dispersing and drying and / or firing the inorganic pigment powder without dispersing the inorganic pigment powder therein.

[0041]

Next, the present invention will be described specifically with reference to examples. However, the present invention is not limited to the following examples unless departing from the gist thereof.

Example 1 Tetraethyl silicate
9 mol, 0.01 mol of 3-aminopropyltrimethoxysilicate, 0.01 mol of boron methoxide, and 0.04 mol of zirconium tetra-n-butoxide were dissolved in a mixed solvent of 300 g of ethanol and 90 g of 2-ethoxyethanol. Next, 2.9 mol of acetic acid and 0.03 mol of 60% nitric acid were added to the obtained mixed solution, and the mixture was refluxed. The reflux temperature was set to 80 to 85 ° C., and the state was maintained for 4 hours. Next, 0.02 mol (in terms of SiO ₂ ) of colloidal silica (isopropanol solvent type: manufactured by Nissan Chemical Industries, Ltd.) and 1 mol of water were mixed with 200 g of 2-ethoxyethanol.
And the dilution was added to the reflux. Reflux was further continued, and IR measurement was performed every hour. Thereafter, an absorption peak was confirmed at around 1200 cm ^−1, which is the skeletal vibration of silica, and after continuing the reflux for another 1 hour from the confirmed point, the reaction was terminated to obtain an inorganic polymer compound. 1-Methoxy-2-propanol was added to the obtained inorganic polymer compound to adjust the silica concentration in the inorganic polymer compound to 5% by weight.

(Example 2) Ethyl silicate 40 was added to 0.1%.
5 mol, 1 mol of methyltrimethoxysilicate, γ-
Tacyl propoxy trimethoxy silicate 0.09
, 3-aminopropyltrimethoxysilicate 0.0
2 moles with 100 g of 1-methoxy-2-propanol
It was dissolved in a mixed solvent with 240 g of isopropanol. Next
Then, 3.6 mol of acetic acid and p-toluene were added to the obtained mixed solution.
0.01 mole of sulfonic acid was added. And this is disrupted
While stirring, water 1.7 diluted with 50 g of isopropanol was used.
Mole was added to this and refluxed. The reflux temperature is 80-85
° C and kept in that state for 4 hours. Then obtained
In the reflux, colloid diluted with 200 g of isopropanol was used.
Dalsilica (isopropanol solvent type: Nissan Chemical Industries)
0.2 mol (SiO) _TwoConversion) and zirconium
0.02 mol of tetra-n-butoxide and boron ethoxy
0.001 mol, 1 mol of acetic acid and 0.0% of 50% nitric acid.
And 1 mol of a mixed solution. Further reflux
Subsequently, IR measurement was performed every hour. afterwards. Silica
1020cm which is skeletal vibration^-1Confirm absorption peak near
did. After refluxing for 1 hour from the time when it was confirmed, the reaction was stopped.
finished. Finally, add 0.02 mol of zinc acetate
After dissolution, an inorganic polymer compound was obtained. The obtained inorganic polymer
Add isopropanol to the compound and add
The silica concentration in the medium was adjusted to 5 wt%.

Example 3 Tetraethyl silicate
5 mol, 0.75 mol of methyltrimethoxysilicate,
γ-glycidoxypropyltrimethoxysilicate 0.
0.6 mol, colloidal silica (isopropanol solvent type: manufactured by Nissan Chemical Industries, Ltd.) 0.1 mol (SiO ₂ equivalent), 3-aminopropyltrimethoxysilicate 0.1 mol.
015 mol, zirconium tetraisopropoxide
04 mol was mixed with 200 g of isopropanol, and while stirring the mixture, 2.8 mol of water, 1.2 mol of acetic acid,
0.005 mol of tin tetrachloride in 200 g of isopropanol
Was added, and the mixture was refluxed. The reflux temperature was set to 80 to 85 ° C., and the state was maintained for 4 hours. Then, colloidal silica (isopropanol solvent type:
0.25 mol (made by Nissan Chemical Industries, Ltd.) (in terms of SiO ₂ ) was gradually added, and the mixture was further refluxed, and an IR measurement was performed every hour. Then, 1200 cm which is the skeletal vibration of silica
^{After an} absorption peak was confirmed at around ^-1 and reflux was continued for another 1 hour from the point of confirmation, the reaction was terminated to obtain an inorganic polymer compound. 1-methoxy- was added to the obtained inorganic polymer compound.
2-Propanol was added to adjust the silica concentration in the inorganic polymer compound to 5% by weight.

Example 4 Tetraethyl silicate
8 mol, methyltriethoxysilicate 0.2 mol, M
0.2 mol of S51 (silica condensation polymer manufactured by Mitsubishi Chemical Corporation)
iO ₂ terms), .gamma. methacrylic propoxy trimethoxy silicate 0.08 mol of zirconium tetra n- butoxide 0.08 mol, mixed with ethanol 200 g,
Further, 2.4 mol of acetic acid and 0.02 mol of titanium tetrachloride were added thereto, and the mixture was refluxed. The reflux temperature is 80-85 ° C,
This state was maintained for 4 hours. Next, colloidal silica (isopropanol solvent type: manufactured by Nissan Chemical Industries, Ltd.)
0.05 mol (in terms of SiO ₂ ) and 1.2 mol of water were added and reflux was continued, and IR measurement was performed every hour. afterwards.
An absorption peak was observed at around 1200 cm ^−1, which is the skeletal vibration of silica. After the reflux was continued for 1 hour from the time when it was confirmed, the reaction was terminated to obtain an inorganic polymer compound. 1-Methoxy-2-propanol was added to the obtained inorganic polymer compound to adjust the silica concentration in the inorganic polymer compound to 5% by weight.

Example 5 Tetraethyl silicate
9 mol, 0.02 mol of 3-aminopropyltrimethoxysilicate, 0.08 mol of γ-methacrylpropoxytrimethoxysilicate, 0.02 mol of boron methoxide, 0.05 mol of zirconium tetra-n-butoxide, 300 g of methanol and 2- Methoxyethanol 10
0 g and dissolved in a mixed solvent. Next, 1.5 mol of acetic acid and 0.03 mol of titanium tetrachloride were added to the obtained mixed solution, and the mixture was refluxed. The reflux temperature was set to 80 to 85 ° C., and the state was maintained for 4 hours. Then, colloidal silica (isopropanol solvent type: manufactured by Nissan Chemical Industries, Ltd.) 0.02 mol (SiO ₂ equivalent) water 1.5 mol and was diluted with 2-methoxyethanol 200 g, adding the dilution to the reflux did. Reflux was further continued, and IR measurement was performed every hour. Thereafter, 1200 cm ^−1, which is the skeleton vibration of silica,
An absorption peak was confirmed in the vicinity.
After continuing refluxing for an hour, the reaction was terminated to obtain an inorganic polymer compound. 1-methoxy-2 was added to the obtained inorganic polymer compound.
-Propanol was added to adjust the silica concentration in the inorganic polymer compound to 5 wt%.

Example 6 One mole of ethyl silicate 40
, 1 mol of methyltriethoxysilicate, γ-methacrylate
0.08 mol of rilpropoxytriethoxysilicate,
3-aminopropyltriethoxysilicate 0.02mo
Is added to 100 g of 1-methoxy-2-propanol and
It was dissolved in a mixed solvent with 240 g of propanol. next,
3.6 mol of acetic acid and 0.0% of 60% nitric acid were added to the obtained mixed solution.
1 mol. Then, while stirring these,
1.7 mol of water diluted with 50 g of propanol was added thereto.
And refluxed. The reflux temperature is 80-85 ° C.
And held for 4 hours. Then, the obtained reflux was
Colloidal silica diluted with 200 g of propanol (a
Sopropanol solvent type: Nissan Chemical Industries Ltd.) 0.1
Mol (SiO _TwoConversion) and zirconium tetra n-but
0.05 mol of oxide and 0.005 mol of boron ethoxide
And 1 mol of acetic acid and 0.01 mol of 60% nitric acid
The resulting mixture was added. Continue refluxing every hour
Was subjected to IR measurement. afterwards. It is the skeleton vibration of silica
1020cm^-1An absorption peak was observed in the vicinity. confirmed
After refluxing for 1 hour from the time, the reaction was terminated. Soshi
Finally, 0.02 mol of zinc acetate was added and dissolved,
A molecular compound was obtained. Isotope is added to the obtained inorganic polymer compound.
Silanol concentration in inorganic polymer compound by adding lopanol
Was adjusted to 5 wt%.

Example 7 Tetramethyl silicate
5 mol, 0.75 mol of methyltriethoxysilicate,
γ-glycidoxypropyltriethoxysilicate 0.
06 mol, colloidal silica (methanol solvent type:
Nissan Chemical Industries, Ltd.) 0.1 mol (SiO ₂ equivalent), 3-
0.015 mol of aminopropyltriethoxysilicate and 0.04 mol of zirconium tetraisopropoxide are mixed with 200 g of isopropanol, and while stirring the mixture, 2.8 mol of water, 1.2 mol of acetic acid and 0 mol of tin tetrachloride are added. A mixed solution of 0.005 mol dissolved in 200 g of isopropanol was added, and the mixture was refluxed. The reflux temperature is 80-8
The temperature was kept at 5 ° C. and kept for 4 hours. Next, 0.2 mol (in terms of SiO ₂ ) of colloidal silica (methanol solvent type: manufactured by Nissan Chemical Industries, Ltd.) was gradually added, and the mixture was further refluxed, and an IR measurement was performed every hour. afterwards,
An absorption peak was confirmed at around 1200 cm ^−1, which is the skeletal vibration of silica, and reflux was continued for an additional hour from the point of confirmation, after which the reaction was terminated to obtain an inorganic polymer compound. 1-methoxy-2-propanol was added to the obtained inorganic polymer compound, and the silica concentration in the inorganic polymer compound was reduced to 5 wt%.
Was prepared.

(Comparative Example 1) In Example 1, the reaction was carried out without adding 60% nitric acid as an acid catalyst. Except for this, it was the same as Example 1. As a result of the IR measurement, no absorption peak was observed at about 1200 cm ^−1, which is the absorption peak of SiO ₂ , at the end of the reaction in Example 1. Further, the obtained liquid had poor wettability to the glass substrate.

(Comparative Example 2) The reaction was carried out in the same manner as in Example 2 except that ethyl silicate 40 was used in an amount of 1 mol and no alkylalkoxysilicate was added. Except for this, it was the same as Example 2. After completion of the reaction, when the film adhesion to a substrate coated with a fluororesin and an acrylic resin was examined, peeling was observed.

Comparative Example 3 The reaction was performed in the same manner as in Example 3 except that zirconium tetraisopropoxide and colloidal silica were not added, and the other conditions were the same. The end point of the reaction was confirmed by IR measurement. The obtained inorganic polymer compound was applied to a stainless steel substrate and dried at 100 ° C. for 20 minutes to form a film. A 0.5% sodium hydroxide solution was brought into contact with this film to examine its corrosion resistance (24 hours). As a result, dissolution of the film was observed.

(Comparative Example 4)
And colloidal silica were not added. Except for this, it was the same as Example 4. The obtained inorganic polymer compound was applied to a glass substrate and dried at 100 ° C. for 20 minutes to form a film. The pencil hardness of this film is measured by a pencil hardness test (JIS K
5H) was 3H.

Comparative Example 5 The reaction was carried out in the same manner as in Example 5 except that the amount of boron methoxide was changed to 0.4 mol, and the other conditions were the same. The obtained inorganic polymer compound was applied to a glass substrate and dried at 100 ° C. for 20 minutes to form a film.
The pencil hardness of this film was measured using a pencil hardness test (JIS K540).
0) was 3H. A 0.5% sodium hydroxide solution was brought into contact with this film to examine its corrosion resistance (24 hours). As a result, dissolution of the film was observed.

(Comparative Example 6)
The reaction was carried out at room temperature without reflux under the appropriate conditions. Obtained
The liquid was measured by IR,_TwoIs the absorption peak of
1200cm ^-1No absorption peak is observed near
Was. In addition, the resulting solution has an acetic acid odor, and the reaction proceeds.
It was confirmed that it did not.

Comparative Example 7 In Example 7, the added amount of γ-glycidoxypropyltriethoxysilicate was 0.4 mol, and the added amount of 3-aminopropyltriethoxysilicate was 0.2 mol. Except for this, it was the same as Example 2. The obtained inorganic polymer compound was applied to a glass substrate and dried at 100 ° C. for 20 minutes to form a film. The pencil hardness of this film was measured using a pencil hardness test (JIS K 5400).
Was 2H.

(Experimental Example 1) The inorganic high molecular compounds obtained in Examples 1 to 7 were applied onto a glass substrate, a stainless steel substrate, and a substrate on which a fluororesin coating film was formed, respectively. For 20 minutes to form an inorganic polymer compound film. Each of the obtained inorganic polymer compound films was subjected to a tape peeling test (JIS K5400) and a pencil hardness test (JIS K5400). Table 1 shows the obtained results. For comparison, Comparative Example 1
Films were similarly formed using the compounds obtained in Nos. To 7, and the same test was performed. Table 1 also shows the obtained results.

[0057]

[Table 1]

As shown in Table 1, all of Examples 1 to 7 have good tape peeling test results, and the film has excellent adhesion to any of glass, stainless steel, and fluororesin coatings. It was confirmed that. In addition, the pencil hardness was 6H or more in all cases, and it was confirmed that the film had a sufficient film hardness. On the other hand, in the case of Comparative Examples 1 to 7, it was found that the hardness of the film formed on the stainless steel or fluororesin coating film was particularly low.

(Experimental Example 2) Inorganic polymer powders obtained in Examples 1 to 7 were dispersed with respective inorganic oxide powders of ITO powder, titanium oxide and zinc oxide as inorganic pigment powders. In the same manner as in 1, an inorganic polymer compound film was formed. In this example, only a glass substrate was used as the substrate. The amount of the inorganic oxide powder added to the inorganic polymer compound is expressed in terms of weight,
O ₂ : inorganic oxide powder = 1: 1. A tape peeling test (JIS K 5400) and a pencil hardness test (JIS K 5400) were performed on the obtained inorganic polymer compound film in the same manner as in Experimental Example 1. Table 2 shows the obtained results. Also, for comparison, Comparative Examples 1 to 7
In the same manner, films were formed with the compounds obtained in the above, and the same test was performed. The obtained results are also shown in Table 2.

[0060]

[Table 2]

As shown in Table 2, all of Examples 1 to 7 have good tape peeling test results.
It was confirmed that the adhesion of the film was excellent regardless of whether titanium oxide or zinc oxide was dispersed. Further, the pencil hardness was 5H or more in all cases, and it was confirmed that the film had a sufficient film hardness. On the other hand, it was found that the films of Comparative Examples 1 to 7 had lower overall film hardness than those of Examples 1 to 7.

[0062]

As described above, according to the method for producing an inorganic polymer compound of the present invention, a predetermined amount of each of the above-mentioned materials is used, and these are partially or wholly refluxed, and finally the entire amount is mixed. Therefore, it is possible to improve the wetting of the obtained inorganic polymer compound on the substrate.

The inorganic polymer compound of the present invention obtained by this method is coated on a substrate and dried and / or calcined to obtain excellent functions such as adhesion and corrosion resistance. A film can be formed.

Further, the inorganic polymer compound film of the present invention obtained from this inorganic polymer compound has excellent functions such as adhesion and corrosion resistance. Since it can be dispersed, various applications can be provided by providing various characteristics, for example, a conductive inorganic film can be obtained by dispersing a conductive inorganic powder.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 3/36 C08K 3/36 5/09 5/09 C08L 83/02 C08L 83/02 85/00 85 / 00 85/04 85/04 C09D 1/00 C09D 1/00 5/00 5/00 Z 183/00 183/00 185/00 185/00 (72) Inventor Chiemi Shimizu 3 Higashinodacho, Miyakojima-ku, Osaka-shi, Osaka No. 2-33 Fuji Chemical Co., Ltd. (72) Inventor Hiroki Imai 3-2-33 Higashi Nodacho, Miyakojima-ku, Osaka-shi, Osaka Prefecture Fuji Chemical Co., Ltd. 3-33 Higashi Noda-cho Fuji Chemical Co., Ltd. (72) Tadashi Ono 1-3-2 Shibaura, Minato-ku, Tokyo Shimizu Construction Co., Ltd. (72) Tomoji Fujita 1-chome Shibaura, Minato-ku, Tokyo No. 2-3 Shimizu Corporation F-ta None (reference) 4F100 AA00A AA20A AA25H AA33H AB04B AG00B AK17B AK52A AT00B BA02 BA10A BA10B CA13A CC00A DE01A DE01H EH46A EH462 EJ482 EJ862 GB90 JB02 JK06 4G072 AA25 BB09 EE06 FF01 FF02 FF04 GG03 HH18 HH30 JJ45 JJ46 KK01 LL15 MM40 NN21 PP20 RR05 RR30 4J002 CP02W CQ00X CQ02X DJ016 FD016 FD207 HA08 4J030 CA01 CC06 CC15 CC16 CD11 CE02 CE11 CG20 4J038 DL021 DL032 DL052 DL082 DL112 DL122 DM022 HA096 HA126 HA156 HA166 HA336 HA446 JA19 JA26 JA43 J43 JC13 KA06 KA08 MA06 NA03 NA12 NA20 PA21

Claims (4)

[Claims] 1. The general formula Si (OR ¹ ) ₄ : (wherein R ¹
Represents an alkyl group having 1 to 4 carbon atoms) and a general formula R ² Si (OR ³ ) ₃ :
(Where R ² Is an alkyl group having 1 to 8 carbon atoms, and R ³ is an alkyl group having 1 to 4 carbon atoms), and 2 is selected from a silica condensation polymer
Per 1 mol of the species or the total number of moles of the general formula Zr (OR ^{₄₎ 4} :( wherein R ⁴ is C2-4
And / or a Zr alkoxide represented by the general formula B (OR ⁵ ) ₃ : wherein R ⁵ has 1 to 1 carbon atoms.
B alkoxide represented by the following formula ( ₂ ): 0.05 to 0.2 mol; silica sol: 0.01 to 0.3 mol in terms of SiO ₂ ; acid and / or metal salt: 1/100 １ ／ 1/30 mol, water and / or acetic acid 1 to 4 mol, and a hydrophilic organic solvent are prepared, and then these materials are partially or entirely refluxed,
A method for producing an inorganic polymer compound, wherein the whole amount is finally mixed. 2. An inorganic polymer compound obtained by the method for producing an inorganic polymer compound according to claim 1. 3. An inorganic polymer compound film, which is a film formed by applying the inorganic polymer compound according to claim 2 on a substrate, drying and / or baking. 4. The inorganic polymer compound film according to claim 3, wherein an inorganic pigment powder is dispersed in the inorganic polymer compound, and is applied on a substrate in that state.